Anthracene dyes and process of making them.



HUGO WCPLFF AN'D FILI'P KAGER, F MAIN'NHEIM, GERMANY, ASSIGNORS '10BADISCHE KNILIN'85 SODA FABRIK, OF LUDWIGSHAEEN-ONTHE-RHINE, GER-MANY, ACORPO- RATION.

ANTHRAGENE DYESAND PROCESS OF MAKING- THEM.

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thraquinone bodies, under which term we imciude l-a'cetyl-aminoanthraquinone or a derivative thereof or mixture of these compounds withone another or with other acetyl-amino-anthraquinones, by treatment withan acid chlorid as described, for in-' stance in Letters Patent Nos.863,401 and 925,917, can, by treating at temperature of at least about140 C. with a compound capable of extracting the elements of water, beconverted into new products which constitute vat coloring matters anddye vegetable fiber generally strong yellow-brown to deep red-brownshades of excellent fastness. For the purpose of extracting the elementsof water according to our invention, concen- .trated sulfuric acid isespecially suitable.

The said intermediate products can also be converted into the new vatcoloring matters by a more energetic treatment with, acid chlorid thanthat described in the specifications of the aforesaid patents,that is tosay, the new vat coloring matters can be prepared by subjecting one, orseveral, of the said 1 acetyl-amino-anthraquinone compounds to aprolonged treatment with an acid chlorid, employing if necessary ahigher temperature, so that the dehydration takes place. Further, ifdesired, the production of theacetylamino-anthraquinone from theamino-anthraquinone and acetic anhydrid, acetyl chlorid, or sodiumacetate, can be carried out at the same time.

Qur new compounds are characterized by the following properties: Theyconsist, when dry, of from yellow-brown to red powders which areinsoluble in water and in dilute alkalis, they yield from red-brown tored solutions in concentrated sulfuric acid and'brown solutions inboiling glacial acetic acid and nitrobenzene; with alkaline hydrosulfitethey give rise to from yellowred to .red-brown 'vats which dye' cottonfrom reddish brown to yellowish brown Specification of Letters Patent.Patented liIay 21 1918,

v hpplicatio n filed. December 4, 1913. Serial No. 804,731.

shades, which shades upon treatment with a neutral solution of sodiumhydrosulfite remain unchanged.

The following examples will serve to illustrate further the naturev ofour invention, but the invention is not confined to these examples. Theparts are by weight:

Example 1 Heat together, for from 1 to 2 hours, at about fronprl lO to160 (1, one hundred and fifty partsbf concentrated sulfuric acid and 10parts of the condensation product obtainable froml-acetyl-aminoanthraquinone and phosphorus xychlorid by boiling until ayellow crystalline mass is obtained, then treating the mass with waterand filtering oil the product and drying it (see Example 1 of Patent No.863,401). When the mixture is cold, pour it into water, raise to theboil, filter, wash while hot and, if desired, extract thecoloriug matterwith boiling dilute sodium carbonate solution. The coloring matter thusobtained consists of a dark red paste which is insoluble in dilute acidsand alkalis. It gives u red-brown solution in concentrated sulfuric acidand a. brown solut.on in boiling glacial acel ic acid or nitrobenzene.It yields a red-brown vat with alkaline hydrosulfite solution and dyescotton reddish brown shades of excellent. fasrness.

()n treating, in a similar manner, the product obtained from a mixtureof 67 parts of l-acciyl-amino-anthraquinone and 100 parts of(iiacetyl-di-amino-anthraquinone (obtainable by reducing and thenacetylating the a-rlinilro-anthraquinone described in the specificationof German Patent 72685) by boiling with 334 parts of phosphorusoxychlorid during about ten minutes a product is obtained which appearsvery similar to that obtained as above described.

li'wwmple f5.

'lreat, in the i'nunner described in the foregoing example thecondensation product obtained by boiling together, for about tenminutes, in a reflux ap 'iaratus, one part of 1-acctyhumine-ant]iraquinone, one part of 2- acetyl-amino-anthraquinoneand four parts of phos 'ihorus oxyi'zhlorid, then treating with. water,filtering, washing and drying.

The product obtained by treating this body with sulfuric acid in theaforesaid mauner, consists of a yellow-brown powder which yields a redsolution in concentrated sulfuric present invention be nets of1-acetyl-amino-anthraquinones described in the specifications of thePatents 863,401 and 925,917.

Instead of separating the condensation products obtainable by treatmentof l-acetylamino-anthraquinone with acid chlorid, the crude reactionmass can according to the for the production of further condensationproducts.

Example Treat a mixture of l-acetyl-amino-anthra quinone anddiacetyl-amino-anthraquinone with phosphorus oxychlorid as describedabove at the end of Example 1 and then subject the mixture to a moreenergetic treatment than described in Example 4; of the specification ofPatent 925,917, for instance heat it for about 3 hours at from 140 to150 G. Then work up the mass as described inthe foregoing Example-1. Thecoloring matter obtained dyes cotton, from a vat, brown shades, whereasthe product of the aforesaid Example 4 of Patent No. 925,917 yieldsorange-red shades.

Now what we claim is 1. The process of producing coloring mattersof theanthracene series by treating, at

a, temperature of at least about 140 (1, with a compound capable ofextracting the elements of water, an intermediate product obtainablefrom a l-acetyl-amino-anthraquinone by treatment with an acid chlorid.

2. The process'of producing coloring matters of the anthracene series bytreating, at a temperature of at least about 140 0., with a compoundcapable of extracting the elements of water, an intermediate productobtainable from a plurality of acetylated am1no-anthraqu1none compoundscontaining immediately employed- .by boiling1-acetyl-amino-anthraquinone with phosphorus oxychlorid, washing theproduct with water and drying it.

Al. The new vat coloring matter obtainable by extracting the elements ofwater from the intermediate products obtainable from a LacetyLamino-anthraquinone body and an acid chlorid, which new vatcoloring matters consist, when dry, of from yellow-brown to red powderswhich are insoluble in water and in dilute 'alkalis, which yield fromred-brown to red solutions in concentrated sulfuric acid and brownsolutions in boiling glacial acetic acid and nitrobenzene, which giverise with alkaline hydrosulfite to form yellow-red to red-brown vatwhich dye cotton from reddish brown to yellowish brown shades, whichshades upon treatment with a neutral solution of sodium hydrosulfiteremain unchanged.

5. Thenew by extracting the elements of water from the intermediateproducts obtainable from 1- acetyl-amino-anthraquinone and phosphorusoxychlorid, which new vat coloring matter consists when dry or a redpowder which is insoluble in water ,and in dilute alkalis, which yieldsa red-brown solution in concentrated sulfuric acid and a brown solutionin boiling glacial acetic acid or nitrobenzene, and which yields ared-brown vat with alkaline hydrosulfite reddish brown shades, whichshades, on treatment with neutral sodium hydrosulfite solution, remainunchanged.

In testimony whereof we have hereunto set our hands in the presence oftwo subscribing witnesses.

J. ALno LLOYD, S. S. BERGER.

vat coloring matter obtainable solution and dyes cotton

